New colouring process



2,944,810 :NEW conounmo rnocnss .JohnReginald Atkinson, Gerald Booth,Eric Leslie Johnsomand Walter Percival "Mills, Manchester, England,assignors to Imperial Chemical Industries Limited, London, England, ,acorporation of Great Britain INmDlltlWing. :liiledzSept. 24,1958, Ser.No. 762,911

(ilaims riority, application GreatBritain Oct. 4, 1957 8 Claims. (fillis-39) This invention relates ,to a new colouring process and moreparticularly it relates to anew process for the production of fastcolourations on textile materials made from synthetic polymers.

It has been found that water-insoluble anthraquinone dyestuffscontaining allgyl groups substitutedby epoxy, chloroorbromogroups whenapplied from aqueous dispersion to 'textile materials made fromsynthetic 'polymers, for example polyamides and basically modifiedpolyacrylonitriles, give colourations of unexpectediy high "fastness towet treatments. 'Colourations effected on these textile grnaterials bythe use of water-insoluble anthraquinonedye-stuffs not containing thesegroups are .in general deficient indastness to wet treatments, and thecolourations obtained'by use of water-insoluble anthraquinone dyestuffscontaining these groups are markedly superior in iastness to wettreatments not only'in that they retain their strength ;of -shade betterbut also in that staining of adjacent textile materials ismuchre-.duced. It seems probabl tha thisia tnessi du tl a t in part to chemicalreaction of the 'dyestufi with the textile material.

Ac or ing o't e e t o erefor ther i pro ided a process for thecolouration of synthetic polymeric textile materials which. comprisestreating the synthetic polymeric textile material with a water-insolubleanthgaouinone dyestuff containing :at'least one epoxyallgoxy, halqg alky, epoxyalkylamino Q ,h oser alkylem group which is 'direc'tlyattachedto a carbon atom of the anthraquinone nucleus or,is,.at tached to acarbon atom of the anthraquinone nucleus through 7 an, a'llgoxy,alkylamino or arylamino radical.

' The 'halogenoalkoxy, epoxyalkoxy, ,epoxyalkylaminoor'halogen-alkylamino groups present in thewater-insoluble anthraquinonedyestuffs may'befurther substituted by hydroxy, alkoxy or hydroxyalkoxysubstituents which are attached to the carbon atoms present in the saidgroups. Asspecific examples of the halogenoalkoxy, epoxyalkoxy,epoxyalkylamino or =--halogerioall ylamiho groups, *which --m-ay bepresent in the --water-insoluble anthraquinone "dyestuffs-ashereinbefore defined, there may be -mentioned B'vy-epoxypropoxy, BZ'-ePOXYPIOPYI- amino,'-'y-chloropropoxy, y-chloropropylamino, 'ybromopropoxy, 'y-bromopropylamino,fi-chloroethoxy,"ii-chloroe'thylarnino, 18-bromoethoxy,18-bromoethylamino, ehloro-dhydroxypropoxy, 'y chloro [3-hydroxypropylamino, 'y-bromo-fl-hydroxypropoxy and 'y-bro no-fl-hy-'droxypropylamino.

'When the epoxyalkylamino or halogenoalkylamino group is atta'chedto acarbon atomof the anthraquinone nucleus through an alkoxy, a'lkyla-mino;or ary1an ino radical the hydrogen atom attached to the-nitrogen atompresent --inthe epoxyalkylamino tor. h alogenoalkylamino h dr a tbyl.balo bncstb l, b lb enqp bpyl,

2,944,870 infes ed Ju y .1 1:969

2 group ca b P Il by a su t t ted o un ubs i uted h ro a qa As eram lesf sash s bs 5.1 or n bs e vh s r s b r ica s here ma be ment on me hyleth l :PEQPYL c clobe y benzy a a exam e o t e a kax k amino-o a yl mincca t er ma msn bnsdst b eth a n an aniline.

Th watb r ns ubl an ra i nc dycs' uff a herea e b defined o m xt r hbre.mayi arpl ed t a yn h ti PQWm f He ma a by a dye n .9 printing processand it ispreferred .to .usethe water-inso u l mbbi b b tnfiin fi te m-oana usous dispersion or a re-dispersiblepowdep The agueousdispersion ofthe water-insoluble anthraquinone dyestufi m be Qb ai s el-mil n th d sefi in wa in the presence of a dispersing agent, for examplefihe radiu s0f s lrbbn lsd a rh belan ib maldeb db condensation products,sulphosuccinic acid esters, 'lfurlgey red oil and condensation productsof 'alkylphenols with ethylene oxide, and if desired inthe presence of aprotective colloid, for example dextn'n. If desired the aqueousdispersion .so obtained .may be converted to a re-dispersible powder ;byany of the processeszknown for-forming re-dispersible powders. l

The application of the water-insoluble -.anthraquinone dyestuiff, ashereinbeit'ore defined, to the synthetic polymeric textile material by adyeing process may be carried .out by immersing the syntheticdpolymerictextile material in a dyebath containing-an.aqueousdispersion of thewater insoluble .anthraquinone dyestufi valid-heating at a temperatureat or near the boilingvpoint ofhthe dyebath, tor; example at atemperature between 7.5 and C. If desired the dyebath can beheatedattemperatures above 100 'C.,-for example ata. temperature between100,and 130 C. under super-atmospheric .pres sure. The:dyed-textilematerial isthen removed .i rom theadyebath, rinsed inwaterand dried.

The water-insoluble anthraquinone-dyestutfs, .ashereinbefore defined,may ,alsoxbeappliedcto thesynthetic polymericntexti le material by aprinting processwhich may be effected by printing the v.syntheticpolymeric textile material with a thickened printing vpaste .containingan aqueous dispersion of the 'anthraquinonerdyestutf. The -p rintingpaste rnayube thickened-with any of the usual thickening agents, forexample methyl cellulose, starch locust been gum, Nafka crystal I gumorssodium alginate, and may contain normal.adjuyants fonprinting pastessuch asurea, thiourea or thiodiglycol .or adjuvants used for theapplication of water-insoluble dyesssuchas methylated spirits, sodiumm-nitrobenzenesulphonate or aqueous emulsionsof sulphonated oils.

The printing paste may be conveniently applied .todhe syntheticpolymeric textile .material by {printing :with block, spray, stencil,screenonroller,,preferablydrying the printed material, and if desiredsteaming at atmospheric pressure or in a closed vessel atsuper-atmospheric pressure when a temperature above .100 C., preferablybetween and C. is required.

As examples of synthetic polymeric textile materials which may be usedin the process of the invention there may be mentioned textile materialscomprising polyamides, for example polyhexamethylene adipa-rnide and thepolymer from caprolactam, and modified polyacrylonitriles.

The water-insolubleanthraquinonedyestufis, as herev V 3 inbeforedefined, used in the process of the invention may be obtained by methodsdescribed in the literature or used in practice for the preparation ofcompounds I containing the groups defined above.

For example those water-insoluble anthraquinone dyestufis containing a'y-ChlOTO or 'y-bromo-hydroxypropylamino group may be obtained byreacting the corresponding anthraquinone compound containing a primaryor secondary amino group with epichlorohydrin or epibromohydrinrespectively. Those water-insoluble anthraquinone dyestufis containing ahalogenoalkylamino or halogenalkoxy group may be obtained by reactingthe corresponding anthraquinone compound containing a hydroxyalkylaminoor hydroxyalkoxy group with a halogenating agent. Those water-insolubleanthraquinone dyestuifs containing a *y-ChlOIO- orv-bromo-B-hydroxypropoxy group may be obtained by reacting thecorresponding anthraquinone compounds containing a hydroxy group withepichlorohydrin or epibromohydrin respectively. Those water-insolubleanthraquinone dyestuffs containing an epoxypropoxy or epoxypropylaminogroup may be obtained by reacting the corresponding anthraquinonedyestutf containing a 3-chloro-2-hydroxypropoxy or3-chloro-2-hydroxypropylamino group with potassium hydroxide.

As specific examples of the water-insoluble anthraquinone dyestufis, ashereinbefore defined, which may be used in the process of the inventionthere may be mentioned 1:4 di(N 'y chloro flhydroxypropylamino)-anthraquinone,

1 :4-di- ,B-chloroethylamino) anthraquinone,

1 :4-difi-bromoethylamino) anthraquinone,

1 {3 chloroethylamino 4 'y chloro 18 hydroxypropylamino-anthraquinone,

1 B bromoethylamino 'y chloro B hydroxypropylaminoanthraquinone,

1 ,8 hydroxyethylamino 4 'y chloro B hydroxypropylaminoanthraquinone,

1 methylamino 4 'y chloro B hydroxypropylaminoanthraquinone,

1 ethylamino 4 'y bromo e hydroxypropylarninoanthraquinone,

l :4-di -bromopropylamino) anthraquinone,

1 :4-di 'y-bromo-/3-hydroxypropylamino) anthraquinone,

1-methylamino-4-;8-bromoethylaminoanthraquinone,

1 {i bromoethylamino 4 q/ bromo B hydroxypropylarninoanthraquinone,

1-isopropylamino-4-p-bromoethylaminoanthraquinone,

1 amino 4 (4' 7 chloro B hydroxypropoxyanilino) anthraquinone,

1 amino 2 bromoethoxy 4 hydroxyanthraquinone,

1 amino 2 p" (13 iodoethoxy)ethoxy 4 hydroxyanthraquinone,

1 amino 2 [8" (,8' bromoethoxy)ethoxy 4 hydroxyanthraquinone,

1 methylamino 4 [4' N:N di ('y chloro )8- hydroxypropyl) aminoanilino]anthraquinone,

1 'y chloro fl hydroxypropylamino 4 [4 N:N- di('y chloro Bhydroxypropyl)aminoanilinol anthraquinone and 1:4 di[3' N:N di('y chloro5 hydroxypropyl) aminoanilinolanthraquinone.

By the process of the invention there are produced on the syntheticpolymeric textile materials red, blue and green shades possessingexcellent fastness to washing.

A preferred class of the water-insoluble anthraquinone dyestuffs ashereinbefore defined for use in the process of the invention are thosewater-insoluble anthraquinone dyestuffs which contain at least onehalogenoalkylamino group directly attachedio a carbon atom of theanthraquinone nucleus, as such dyestufis have excellentafiinity forsynthetic polymeric textile materials.

. 4 a The invention is illustrated but not limited by the followingexamples in which parts and percentages are by weight.

Example 1 1 part of l:4-di(N-v-chloro-B-hydroxypropylamino)anthraquinone is dispersed in 20 parts of water by milling in thepresence of a sodium salt of a sulphonated naphthalene formaldehydecondensation product and the dispersion so obtained is added to 4,000parts of water containing 4 parts of a condensate of ethylene oxide witha fatty alcohol. 100 parts of polyamide textile material are placed inthe dyebath so obtained and the dyebath is then heated to 95 C. andmaintained at that temperature for 60 minutes. The polyamide textilematerial is then rinsed in water, immersed for 30 minutes in a hotaqueous solution containing 0.2% of sodium carbonate and 0.1% of acondensate of ethylene oxide with an alkyl phenol, again rinsed in waterand dried. The polyarnide textile material is dyed a blue shadepossessing very good fastness to washing.

Example 2 1 part of l:4-di(N-y-chloro-fi-hydroxypropylamino)anthraquinone is dispersed in 20 parts of water as described in Example1 and the dispersion so obtained is added to 4,000 parts of Watercontaining 1.5 parts of oleyl sodium sulphate "at 50 C. 100 parts of thebasically modified polyacrylonitrile fibre manufactured by theChemstrand Corporation and sold under their trademark Acrilan are placedin the dyebath so obtained and the dyebath is then heated to atemperature between 98 C. and 100 C. and maintained at that temperaturefor 60 minutes. The modified polyacrylonitrile fibre is then rinsed inwater, immersed for 30 minutes in a hot aqueous solution containing0.05% of sodium carbonate and 0.2% of a condensate of ethylene oxidewith an alkyl phenol, again rinsed in water, and dried. The modifiedpolyacrylonitrile fibre is dyed a blue shade possessing very goodfastness to wet treatments.

Example 3 20 parts of a 5% aqueous dispersion ofl:4di(N-'ychloro-fi-hydroxypropylamino)anthraquinone are mixed with 10parts of urea, 2 parts of an aqueous emulsion of sulphonated sperm oiland pine oil, 1 part of sodium m-nitrobenzenesulphonate, 7 parts ofwater and 60 parts of a 30% aqueous solution of Nafka crystal gain. Theprinting paste so obtained is applied from a roller printing machine toa polyamide textile material. The polyamide textile material is driedand then exposed for 15 minutes to steam at atmospheric pressure. Theprinted polyamide textile material so obtained is rinsed in cold waterand soaped at C. in a solution containing 2 parts of soap in 1000 partsof water. The printed polyamide textile material is then rinsed in waterand dried. A bright blue print is obtained which has excellent fastnessto washing and to light.

Example 4 1, part of l:4-di(N- -chloro-p-hydroxypropylamino)anthraquinone is dispersed in 20 parts of water as described in Example1 and the dispersion so obtained is added to 4000 parts of watercontaining 4 parts of a condensate of ethylene oxide with a fattyalcohol. 100 parts of the polymerised caprolactam textile material areplaced in the dyebath so obtained and the dyebath is then heated to C.and maintained at that temperature for 60 minutes. The textile materialis then rinsed in water, im-

'mersed for 30 minutes in a hot aqueous solution con taining 0.2% ofsodium carbonate and 0.1% of 'a condensate of ethylene oxide with analkyl phenol, again rinsed in water and dried. The textile material isdyed a blue shade of very good fastness to washing.

The following table gives further examples of the shades obtained onpolyamide textile materials when the Shade on poly- ExampleAnthraqutnone Dyestufi amide textile materials1:4-dl(fi-chloroethylam1no)anthraquinone Reddlsh-blue. 1 -Bhydroxyethylamino 4 'y chloro 5- Do.

hydroxypropylamino anthraquinone. 1:4 di('y bromopropylamino)anthraqui-D0.

none. 1 methylamlno 4 B bromoethylamtno- Do.

anthraquinone. 9 1 amino 4 (4- 7 ehloro B hydroxy- Do.

propylanlllno)anthraqui.none. l 1 amino 2 B bromoethoxy 4 hydroxy-Bluish-red.

anthraquinone. l1 l-methylamino-4-[4-N:N d1 ('y-ch1oro-B- Greenlsh-blue.

hydroxypropyl)aminoanilino1anthraqulnone. 12 1 'y chloro fihydroxypropylamlno 4- Do.

[4- N: N d1('y-chIoro-fl-hydroxypropyl)- aminoanilinohnthraqulnone.

What we claim is:

1. Process for the coloration of synthetic polymeric textile materialsselected from the class consisting of polyamide and modifiedpolyacrylonitrile textile materials which comprises treating the saidsynthetic polymeric textile materials with a water-insolubleanthraquinone dyestufi containing at least one group selected from theclass consisting of w-oxiranylalkoxy, whalogenoalkoxy,w-oxiranylalkylarnino, and w-halogenoalkylamino, each group beingattached to a carbon atom of the anthraquinone nucleus through a memberselected from the class consisting of a direct link, an alkoxy radical,an alkylamino radical, and an arylamino radical.

2. Process as claimed in claim 1, wherein said dyestutf has anw-halogenoalkoxy group which also contains a carbinol group vicinal tothe w-carbon atom.

3. Process as claimed in claim 1, wherein said dyestulf has anw-halogenoalkylamino group which also contains a carbinol group vicinalto the w-carbon atom.

4. Process as claimed in claim 1, wherein said waterinsolubleanthraquinone dyestufi' contains a 'y-chloro-phydroxypropylamino group.

5. Process as claimed in claim 1, wherein said waterinsolubleanthraquinone dyestufi contains a q -bromo-phydroxypropylamino group.

6. Process as claimed in claim 1, wherein said waterinsolubleanthraquinone dyestulf is supplied to the synthetic polymeric textilematerial by dyeing.

7. Process as claimed in claim 1, wherein said waterinsolubleanthraquinone dyestutf is applied to the synthetic polymeric textilematerial by printing.

8. Synthetic textile materials selected from the class consisting ofpolyamide and modified polyacrylonitrile textile materials colored witha water-insoluble anthraquinone dyestulf containing at least one groupselected from the class consisting of w-oxiranylalkoxy,w-halogenoalkoxy, w-oxiranylalkylamino, and w-halogenoalkylamino, eachgroup being attached to a carbon atom of the anthraquinone nucleusthrough a member selected from the class consisting of a direct link, analkoxy radical, an alkylamino radical, and an arylamino radical.

No references cited.

1. PROCESS FOR THE COLORATION OF SYNTHETIC POLYMERIC TEXTILE MATERIALSSELECTED FROM THE CLASS CONSISTING OF POLYAMIDE AND MODIFIEDPOLYACRYLONITRILE TEXTILE MATERIALS WHICH COMPRISES TREATING THE SAIDSYNTHETIC POLYMERIC TEXTILE MATERIALS WITH A WATER-INSOLUBLEANTHRAQUINONE DYESTUFF CONTAINING AT LEAST ONE GROUP SELECTED FROM THECLASS CONSISTING OF W-OXIRANYLALKOXY, W HALOGENOALKOXY,W-OXIRANYLALKYLAMINO, AND W-HALOGENOALKYLAMINO, EACH GROUP BEINGATTACHED TO A CARBON ATOM OF THE ANTHRAQUINONE NUCLEUS THROUGH A MEMBERSELECTED FROM THE CLASS CONSISTING OF A DIRECT LINK, AND ALKOXY RADICAL,AN ALKYLAMINO RADICAL, AND AN ARYLAMINO RADICAL.